Size composition for glass, and treated glass structures and method for manufacturing same



United States Patent 3,262 809 SIZE COMPOSITION FORGLASS, AND TREATEDGLASS STRUCTURES AND METHOD FOR MAN- UFACTURING SAME Jesse Irwin Aber,Newark, Ohio, assignor to Owens- Cormng Fiberglas Corporation, acorporation of Delaware No Drawing. Continuation of application Ser. No.476,548, Dec. 20, 1954. This application June 29, 1962, Ser. No. 206,197

18 Claims. (Cl. 117-72) This is a continuation of my copendingapplication Ser. No. 476,548, filed December 20, 1954, entitled, SizeComposition for Glass, and Treated Glass Structures and Method forManufacturing Same, now abandoned.

This invention relates to structures formed of combinations of syntheticorganic resinous materials and glass, such as glass fibers or thinflexible films of glass in which the surfaces of the glass are treatedwith a size composition to improve the performance and processingcharacteristics of the glass and to render the surfaces of the glassbodies more receptive to the resinous materials and more easily andrapidly wet out by the resinous materials employed in combinationstherewith in the manufacture of coated fabrics, reinforced plastics andlaminates.

Modification of the surfaces of the glass bodies to make them morereceptive to the resinous materials achieves the desired improvement inthe ability of the resinous material rapidly and completely to wet outthe glass surfaces and the development of a stronger and more permanentbonding relation between glass and resin in the manufacture of thedescribed structures.

Without pre-treatment of the surfaces of the glass fibers or other glassfilm to make them more receptive to the resinous materials employed incombinations therewith, it is difficult to achieve satisfactory coverageof the glass and it has been found to be relatively impossible todevelop a sufiicient degree of bonding between the resinous material andthe glass because the groupings that predominate on the glass surfacesrender such surfaces hydrophilic, or water-loving in character and moreor less resinophobic, or repellent to resinous material. As a result,the resinous materials applied to the glass tend to draw away from thesurfaces and form into droplets which can be relatively easily separatedfrom the surface upon drying. Any bonding relation which is establishedis only temporary in nature because a moisture film preferentially formson the glass surfaces, under high humidity conditions, and the moisturefilm separates the resinous material from the glass surfacesubstantially to minimize the bonding relation.

In order to enhance the manufacture of combinations of glass and resin,it is important either to modify the characteristics of the glasssurfaces to convert the hydrophilic surface into one that isresinophilic so that it will be preferentially wet out with the appliedresinous material or else to formulate the resinous material with anagent capable of functioning as an anchoring agent which attaches to thehydrophilic glass fiber surfaces through some components of the compoundwhile other portions are available for attachment to the resinousmaterial. Where the glass fibers or films are fabricated separate andapart from the combinations thereof with resinous material, it isdesirable to employ the first system in which the glass surfaces aremodified and, in which the surfaces are concurrently protected againstdestruction or deterioration prior to their combinations with resinousmaterials. It is in this latter system to which the concepts of thisinvention are directed and it is an object of this invention to produceglass bodies, such as glass fibers and films of glass, sized with thematerial that renders the surfaces resin-ophilic in character, whichlubricates and protects the surfaces against destruction ordeterioration prior to combinations with the resinous materials andwhich hastens the wetting out of the glass surfaces with the resinousmaterials and enhances the manufacture of structures embodying suchcombinations and it is a related object to produce a treatingcomposition for use in same.

It is another object of this invention to produce and to provide amethod for producing treated glass fibers and films of the typedescribed in which the surfaces are more rapidly and completely wet outwith resinous materials used in combinations therewith and in which theglass materials are more effectively combined with such resinousmaterials to enable more efficient manufacture of fibrous structureshaving improved physical and strength characteristics.

Briefly described, this invention is directed to the treatment ofsurfaces of glass with a composition that functions as a size tolubricate and protect the glass surfaces and to achieve more rapid andcomplete wetting out of the glass with resinous materials usuallycombined therewith in the manufacture of reinforced plastics andlaminates. Representative of such resinous materials are thermosettingresins, such as unsaturated polyester resins, epoxy resins, phenolformaldehyde resins, urea formaldehyde resins, melamine formaldehyderesins and the like heat-curable resins. Resinous materials combinedwith glass fibers in the manufacture of coated fabrics may berepresented by polyvinyl chlorides, vinyl chloride-vinyl acetatecopolymers, polyamides, polyalkylacrylates, polyethylene and elastomersof the type butadiene-acrylonitrile copolymers, butadiene-styrenecopolymers, and the like.

A treating composition containing ingredients for producing the desiredcharacteristics on glas fiber surfaces, when applied as a size, isillustrated by the following:

Example 1 2.0 percent by weight of a saturated polyester (Glidden GRV2172) 0.25 percent by weight of the condensation reaction product ofpelargonic acid and tetraethylene pentamine solubilized with acetic acid2.0 percent by weight methacrylato chromic chloride (20% solution inisopropanol, acetone and water) 010 percent by weight polyvinyl alcohol0.02 percent by weight Pluronic F68 (Wyandotte Chemical Company).

These materials are combined in the amounts described with water andadjusted with acetic acid to a pH of between 4.5 and 5.5. It ispreferred to form an aqueous dispersion of the polyester resin withammonium hydroxide or the like amine as the dispersing agent, and thenstabilize the dispersion by the addition of the polyvinyl alcohol. Thesolubilized dispersion can then be converted, if desired, to the acidside by the addition of acetic acid where the cationic amine acetate hasgreater stability. It is preferred to adjust the composition to a pH ofbetween 4.5 and 5.5 but it will be understood that the composition maybe formulated to have either an acid or basic pH, as will hereinafter bepointed out.

Application of the size composition is preferentially made to the baresurfaces of the glass, such as by conventional sizing means including aroller coater, wiping pad or the like when applied to the glass fibersurfaces in forming, or by means of a brush, spray, roller or wiper padwhen applied to fibers or films of glass and the like. If othermaterials have previously been applied to the glass surfaces, such othermaterials should be removed by washing or by burning off before thetreating composition is applied. The treating composition should beapplied in amounts sufiicient to form a substantially continuous coatingon the glass fiber surfaces when dried, such as by air drying. It ispreferred, however, to bake the coating on the surface by exposure totemperatures within the range of 200-300 F. to modify the glass surfacesand to improve the bonding relation of resinous materials subsequentlyapplied in combinations therewith.

The saturated polyester functions as a film former in the treatingcomposition to protect the surfaces of the glass and to improve theprocessing and performance characteristics of glass fibers. It isdesirable to make use of a saturated polyester resin formed of adihydric alcohol and a saturated dibasic acid, otherwise the film formerwill become incompatible with the subsequently applied resinous materialand would therefore present a barrier to the development of the desiredbonding relation between the resinous material and the glass surfaces. Asaturated polyhydric alcohol and a saturated polybasic acid other thanthe dihydric alcohols and dibasic acids may be used as long as thepolyester formulated in the treating composition has been arrested inits reaction before being advanced to an isoluble or infusible statewhen applied to the glass fibers. The amount of saturated polyester inthe treating composition may range from a minimum of 0.25 percent byweight to a maximum of about 5.0 percent by weight of the treatingcomposition.

The polyvinyl alcohol can be used in the treating composition in amountsranging from 0.01 to 0.50 percent by weight of the treating composition.Instead of polyvinyl alcohols, use may be made of other water soluble,water stable, hydrophilic colloids, such as casein, alginates, celluloseethers and esters of the type methyl cellulose, carboxymethyl celluloseand the like, in substantially equivalent amounts as polyvinyl alcoholexcept that less of the alginate or cellulose ether and ester salts willbe required.

The pelargonate amide appears readily to wet out the surfaces of theglass without interfering with the ability of the treated glass fibersurfaces to be rapidly wet out with resinous materials which areafterwards applied in the manufacture of the resinous combinations.Other cationic amine lubricants may be used, such as tetraethylenepentamine reacted to contain 5 methallyl side chains (Arnold Hoffmancompound RL 220), tetraethylene pentamine stearic acid condensateinsolubilized with acetic acid, dicoco fatty acid amine chloride andother long chain organic or fatty acid groups containing an amine or abasic nitrogen atom capable of being formed into salt, quaternaryammonium compound or onium compound. In compositions embodying featuresof this invention, the amine lubricant or other cationic amine lubricantcapable of reacting as an amine is used in concentrations ranging from0.01 to 2.0 percent by weight of the treating composition.

The Pluronic F68 appears to function in preference to many other typesof compounds as an emulsion stabilizer for the treating composition.Technically this type of material may be defined as a co-generic mixtureof conjugated polyoxyethylene-polyoxypropylene compounds containing intheir structure oxypropylene groups and oxyethylene groups on an organicradical derived from a polybasic carboxylic acid having a molecularweight less than 200. The compounds of this type which may be used inthe practice of this invention are characterized in that all of theoxypropylene groups are present in polyoxypropylene chains attached tothe organic radical at the site of a reactive hydrogen atom therebyconstituting a polyoxypropylene polymer. The polyoxyethylene groups areattached to the polyoxypropylene polymer in polyoxyethylene chains. Theaverage molecular weight of the polyoxypropylene polymers in the mixtureis at least 900 and the polyoxyethylene groups represent about 20-90percent by weight of the mixture. The compound Pluronic F68 'has amolecular weight average of about 2000-3000 and is constituted withabout percent oxyethylene groups. Other similar compounds of the typedescribed in US. Patent No. 2,674,619 may be employed. It is preferredto make use of such emulsion stabilizer in concentrations ranging from0.005 to 0.05 percent by weight of the treating composition.

Instead of the methacrylato chromic chloride, use may be made of chromicchloride, but it is preferred to make use of the chromic complexcompounds of the Werner type in which the acido group attached to thenuclear chromium atom is preferably formed with a short chainedaliphatic group or an aromatic group having a short aliphatic group inwhich the aliphatic group contains a highly functional group such as anunsaturated carbon to carbon linkage capable of addition polymerizationor other functional groups such as a group having a high dipole moment,a labile hydrogen atom, or a highly negative group adjacent an availablefree hydrogen. Representative compounds are illustrated in the SteinmanPatent No. 2,552,910. Instead of a chromic complex compound having ashort chained aliphatic or aliphaticaromatic group, use can be made ofchromic complex compounds in which the acido group is represented by anorganic group having more than 8 carbon atoms, particularly whereadditional lubricity is desirable, such as stearato chromic chloride orother Werner compounds of the type described in the Iler Patent No.2,273,040.

The chromic complex, especially compounds having an acido group of shortcarbon length and containing an unsaturated carbon to carbon linkage orother highly functional group, such as methacrylato chromic chloride,methallyl chromic chloride, vinyl chromic chloride and the like, appearsto have a unique quality of stabilizing the emulsion and hardening thefinished cakes of sized glass fibers so that they can be more easilyprocessed into a finished roving and which can be more easily cut in thepreform operation. For this purpose, the chromic complex compound shouldbe employed in concentrations within the range of 0.10 to 10.0 percentby weight of the treating composition.

Where it is desirable to achieve maximum utilization of the strengthproperties of the glass fibers or film in the coated fabric orreinforced plastic or laminate, it is a further concept of thisinvention to make use of an anchoring agent in the form of an organosilicon compound in addition to the chromic complex compound. For suchpurpose, it is preferred to make use of an organo silane or itshydrolysis products having two or more hydrolyzable groups and anorganic group attached directly to the silicon atom containing less than7 carbon atoms in aliphatic arrangement and in which the aliphatic groupcontains an unsaturated carbon to carbon linkage capable of additionpolymerization. The aliphatic group may contain other highly functionalgroups of the type previously described. Representative of such organosilanes is vinyltrichlorosilane, vinyltriacetoxysilane,styryldihydroxysilane, allyltriacetoxysilane and the like. When present,use can be made of the organo silane in amounts ranging from 0.01 to 1.0percent by weight of the treating composition.

Having described the functions of the various ingredients which areformulated together in the manufacture of a treating composition forapplication to glass fibers and the like to improve their processing andperformance characteristics, to improve the bonding relation of theresinous materials employed in combinations therewith and to improve thethoroughness and speed of wetting out of the fibers with the appliedresinous materials and to enhance the materials of the end product,illustration will now be made of formulations both broadly andspecifically of treating compositions which may be used in the practiceof this invention.

Example 2 0.25-5 .0 percent by Weight saturated polyester 0.012.0percent by Weight cationic amine lubricant 0.10-10.0 percent by weightWerner complex compound 0.0l-0.5 percent by weight water soluble, waterstable hydrophilic colloid 0005-005 percent by weight of a co-genericmixture of conjugated polyoxyethylene-polyoxypropylene compounds on apolybasic carboxylic acid having a molecular weight less than 200.

Example 3 025-5 .0 percent by weight saturated polyester 0.01-20 percentby weight cationic amine lubricant 0.102.0 percent by weight Wernercomplex compound 0.010.S percent by weight water soluble, Water stablehydrophilic colloid 0.005-005 percent by weight of a co-generic mixtureof conjugated polyoxyethylene-polyoxypropylene compounds on a polybasiccarboxylic acid having a molecular weight less than 200 001- percent byweight unsatuarted organo silane.

Example 4 2.0 percent by weight saturated polyester (Glidden GRV 2172)2.25 percent by weight tetraethylene pentamine stearate lubricant 0.5percent by weight methacrylato chromic chloride 0.3 percent by weightvinyltrichlorosilane 0.14 percent by weight polyvinyl alcohol 0.02percent by weight Pluronic F68.

The above materials are combined in the desired percentage in water andadjusted to a pH of between 4.5 and 6.

Example 5 3.0 percent by weight saturated polyester 0.5 percent byweight dicoco fatty acid amine chloride 2.0 percent by weight methallylchromic chloride 0.04 percent by weight sodium alginate 0.04 percent byweight of the compound of US. Patent Example 6 2.0 percent by weightsaturated polyester 0.3 percent by weight fatty acid cationic amineacetate 0.4 percent by weight methacrylato chromic chloride 0.4 percentby weight allyltriethoxysilane 0.1 percent by Weight methylcellulose0.03 percent by weight of a co-generic mixture of conjugatedpolyoxyethylene-polyoxypropylene chains on a polybasic carboxylic acidin which the polyoxyethylene groups are present in amounts ranging from20-90 percent by weight and in which the molecular weight is at least900.

Stable compositions of the type embodying features of this invention maybe formulated with the Pluronic F68 and the like conjugatedpolyoxyethylene-polyoxypropylene polybasic carboxylic acid compoundreplaced by alkylene oxide condensation products of dimerized fatty acidalkylol amides of the type described in US. Patent No. 2,470,087,marketed by the American Cyanamid Company under the trade name ofAerotex. These compounds, though not equivalent to the conjugatedpolyoxyethylene-polyoxypropylene polybasic carboxylic acid compounds,may be used in the formulations in amounts ranging from 0.15-2.0 percentby weight and preferably in the amounts of 025-10 percent by weight ofthe materials in the size composition.

Formulations representative of the use of the above materials may beillustrated as follows:

Example 7 2.0 percent by weight of a saturated polyester resin 0.25percent by weight of the condensation reaction product of pelargonicacid and tetraethylene pentamine solubilized with acetic acid 2.0percent by weight rnethacrylato chromic chloride (20% solution) 0.1percent by weight polyvinyl alcohol (medium viscosity grade) 0.25-10percent by weight of the alkylene oxide condensation reaction product ofdimerized linoleic acid alkylol amide.

Materials are combined in the amounts described and diluted with waterand adjusted with acetic acid or other inorganic. or preferably anorganic acid to the desired acidic pH.

Example 8 3.0 percent by Weight of a saturated polyester resin 0.15percent by weight of the condensation reaction product of stearic acidand tetraethylene pentamine solubilized with acetic acid 2.0 percent byWeight of rnethacrylato chromic chloride in 20% solution in isopropanol,acetone and water 0.1 percent by weight polyvinyl alcohol 0.5 .percentby weight AerotexAmerican Cyanamid Company (Patent No. 2,470,081)

94.25 percent by weight Water The alkylene oxide condensation productsof dimerized and trimerized fatty acid alkylol amides appear to confineand protect the particles of saturated polyester resins in the emulsionin a manner to prevent agglomeration or adhesion one to the other uponcontact in the emulsion and thereby markedly to improve the stability ofthe treating composition.

In each of these formulations, the ingredients are combined in thedescribed percentage in water to form an aqueous emulsion which ispreferably adjusted to a pH of between 4.5 ad 5.5 by the addition ofacetic acid or the like acidic medium, if on the basic side, or by theaddition of ammonia or the like amine, if on the acid side.

Treatment may be carried out, as previously described in connection withExample 1 to produce glass fibers and films which are easily and quicklywetted out with unsaturated polyester resins and the like thermosettingresins combined with glass fibers and which develop a satisfactorybonding relation with the treated glass fiber surfaces.

It will be understood that changes may be made in the details of theformulations, their method of application and treatment withoutdeparting from the spirit of the invention, especially as defined in thefollowing claims.

Iclaim:

1. A composition for use in the treatment of glass surfaces forprotecting the surface and for modification of the surface to make itmore easily and completely wettable by resinous materials combinedtherewith in the manufacture of resinous combinations and to improve thebonding relation between the resinous materials and the glass surfaces,consisting essentially of the following ingredients given in percent byWeight:

0.25-50 percent saturated polyester resin in an uncured and solublestate formed of a saturated polyhydric alcohol and a saturated polybasicacid and in which the saturated polyester resin is a partly reactedpolyester resin when formed by reaction of a saturated polyhydricalcohol other than a difunctional alcohol and a polybasic acid otherthan a dibasic acid 0.12.0 percent amine lubricant 01-100 percent Wernercomplex compound, in which the carboxylato group coordinated with thetrivalent nuclear chromium atom contains less than 7 carbon atoms in analiphatic group and in which the aliphatic group also contains a highlyfunctional group 0.010.5 percent water soluble hydrophilic colloid0.005-0.05 percent emulsion stabilizer 99535-8245 percent water.

2. A composition for use in the treatment of glass fibers for protectionof the glass fiber surfaces and for modification of the glass fibersurfaces to make the fibers more readily wettable by resinous materialscombined therewith in the manufacture of resinous combinations and toimprove the bonding relation between the resinous material and the glassfiber surfaces, comprising in percent by weight:

0.25-5,0 percent saturated polyester resin in an uncured and solublestate formed of a saturated polyhydric alcohol and a saturated polybasicacid and in which the saturated polyester resin is a partly reactedpolyester resin when formed by reaction of a saturated polyhydricalcohol other than a difunctional alcohol and a polybasic acid otherthan a dibasic acid 0.12.0 percent amine lubricant 01-100 percent Wernercomplex compound, in which the carboxylato group coordinated with thetrivalent nuclear chromium atom contains less than 7 carbon atoms in analiphatic group and in which the aliphatic group also contains a highlyfunctional group 0.010.5 percent polyvinyl alcohol 0.005-0.05 per-centstabilizer in the form of a co-generic mixture of conjugatedpolyoxyethylene-polyoxypropylene compounds on a polybasic carboxylicacid having a molecular weight less than 200 in which thepolyoxyethylene groups are present in amounts ranging from 20-90 percentby weight of the compound and in which the molecular weight of thecompound is at least 900 99.535-82.45 percent water.

3. A composition for use in the treatment of glass fibers for protectionof the glass fiber surfaces and for modification of the glass fibersurfaces to make the fibers more readily wettable by resinous materialscombined therewith in the manufacture of resinous combinations and toimprove the bonding relation between the resinous material and the glassfiber surfaces, consisting essentially of the following in percent byweight:

0.2S5.0 percent saturated polyester resin formed essentially of asaturated dibasic acid and a dihydric alcohol 0.12.0 percent aminelubricant 01-100 percent Werner complex compound in which the acidogroup coordinated with the trivalent nuclear chromium atom is formedwith an organic group containing less than 7 carbon atoms in aliphaticarrangement and a highly functional group 0.0l-0.5 percent water solublehydrophilic colloid 0.0050.05 percent stabilizer in the form of aco-generic mixture of conjugated polyoxyethylene-polyoxypropylenecompounds on a polybasic carboxylic acid having a molecular weight lessthan 200 in which the polyoxyethylene groups are present in amountsranging from 20-90 percent by weight of the compound and in which themolecular weight of the compound is at least 900 99.535-82.45 percentwater.

4. A- composition for use in the treatment of glass fibers forprotecting the surface and for modification of the surface to make itmore easily and completely wettable by resinous materials combinedtherewith in the manufacture of resinous combinations and to improve thebonding relation between the resinous materials and the glass surfaces,consisting essentially of the following ingredients given in percent byweight:

0.255.0 percent saturated polyester resin formed essentially of asaturated dibasic acid and a dihydric alcohol 01-20 percent aminelubricant 0. 1-1 0.0 percent methacrylato chromic chloride 0.1-0.5percent water soluble hydrophilic colloid 0.0050.05 percent emulsionstabilizer 99535-8245 percent water.

5. A composition for use in the treatment of glass to protect thesurfaces of the glass and to modify the surfaces to make them moreeasily and completely wettable by resinous materials combined therewithin the manufacture of resinous combinations and to improve the bondingrelation between the resinous material and the glass surface, comprisingan aqueous system consisting of the following materials in percent byweight:

0.25-5.0 percent saturated polyester resin in an uncured and solublestate formed of a saturated polyhydric alcohol and a saturated polybasicacid and in which the saturated polyester resin is a partly reactedpolyester resin when formed by reaction of a saturated polyhydricalcohol other than a difunctional alcohol and a polybasic acid otherthan a dibasic acid 0.012.0 percent cationic amine lubricant 0.l2.0percent Werner complex compound in which the carboxylato groupcoordinated with the trivalent nuclear chromium atom contains less than7 carbon atoms in an aliphatic group and in which the aliphatic groupalso contains a highly functional group 0.0l0.5 percent water solublehydrophilic colloid 0.0050.05 percent emulsion stabilizer 0.011.0percent of an organo silane and hydrolysis product thereof in which thesilane has an organic group attached directly to the silicon atom havingless than 7 carbon atoms and containing a highly functional group99.6l5-89.45 percent water.

6. A composition for use in the treatment of glass fibers for protectionof the glass fiber surfaces and for modification of the glass fibersurfaces to make the fibers more readily wettable by resinous materialscombined therewith in the manufacture of resinous combinations and toimprove the bonding relation between the resinous material and the glassfiber surfaces, comprising in percent by weight:

0.255.0 percent saturated polyester resin formed essentially of asaturated dibasic acid and a dihydric alcohol 0.0 1-2.0 percent cationicamine lubricant 0.1-2.0 percent Werner complex compound in which theacido group coordinated with the trivalent nuclear chromium atomcontains less than 7 carbon atoms in an aliphatic group and in which thealiphatic group also contains a highly functional group 0.0l0.5 percentwater soluble hydrophilic colloid 0.005-0.05 percent of a co-genericmixture of conjugated polyoxyethylene-polyoxypropylene compounds on apolybasic carboxylic acid having a molecular weight less than 200 inwhich the polyoxyethylene groups are present in amounts ranging from20-90 percent by weight of the compound and in which the molecularweight of the compound is at least 900 001-10 percent of an organosilane and hydrolysis product thereof in which the silane has an organicgroup attached directly to the silicon atom having less than 7 carbonatoms and containing a highly functional group 99.615-89.45 percentwater.

7. A composition for use in the treatment of glass fibers for protectionof the glass fiber surfaces and for modification of the glass fibersurfaces to make the fibers more readily wettable by resinous materialscombined therewith in the manufacture of resinous combinations and toimprove the bonding relation between the resinous material and the glassfiber surfaces, consisting essentially of the following in percent byweight:

0.25-5.0 percent saturated polyester resin in an uncured and solublestate formed of a saturated polyhydric alcohol and a saturated polybasicacid and in which the saturated polyester resin is a partly reactedpolyester resin when formed by reaction of a saturated polyhydricalcohol other than a difunctional alcohol and a polybasic acid otherthan a dibasic acid 0.01-2. percent cationic amine lubricant 0.1-2.0percent Werner complex compound in which the carboxylato groupcoordinated with the trivalent nuclear chromium atom contains less than7 carbon atoms in an aliphatic group and in which the aliphatic groupalso contains -a highly functional group 0.01-0.5 percent polyvinylalcohol 0.005-005 percent of a co-generic mixture of conjugatedpolyoxyethylene-polyoxypropylene compounds on a polybasic carboxylicacid having a molecular weight less than 200 in which thepolyoxyethylene groups are present in amounts ranging from 20-90 percentby weight of the compound and in which the molecular weight of thecompound is at least 9-00 0.0ll.0 percent of an organo silane andhydrolysis product thereof in which the silane has an organic groupattached directly to the silicon atom having less than 7 carbon atomsand containing a highly functional group 99.61589.45 percent water.

8. A size composition for use in the treatment of glass to protect thesurfaces thereof and to render the surf-aces more receptive to polyesterresins combined therewith in the manufacture of coated fabrics andreinforced plastics in which the size composition consists of thefollowing in percent by weight:

0.25-5.0 percent saturated polyester resin formed essentially of asaturated dibasic acid and a dihydric alcohol 0.01-2.0 percentmethacrylato chromic chloride 0.01-2.0 percent cationic amine lubricant0.0l-0.5 percent polyvinyl alcohol 0.01-l.0 percent of an organo silaneand hydrolysis prodattached directly to the silicon atom containing lessthan 7 carbon atoms and a highly functional group 0.005-005 percent of aco-generic mixture of conjugated polyoxyethylene-polyoxypropylenecompounds on a polybasic carboxylic acid having a molecular weight lessthan 200 in which the polyoxyethylene groups are present in amountsranging from 20-90 percent by weight of the compound and in which themolecular weight of the compound is at least 900 99.6l89.45 percentwater.

9. A glass structure and a coating on the surfaces of the glass toprotect the surface and to render the surface more highly receptive toresinous materials combined therewith in the manufacture ofglass-resinous structures in which the coating comprises the combinationof the following materials in parts by weight:

0.25-5.0 parts saturated polyester resin in an uncured and soluble statefor-med essentially of a saturated dibasic acid and a dihydric alcoholand in which the saturated polyester resin is a partly reacted polyesterresin when formed by reaction of a saturated polyhydric alcohol otherthan a difunctional alcohol and a polybasic acid other than a dibasicacid 0. 1-2.0 parts amine lubricant 0.l-l0.0 parts Werner complexcompound in which the carboxylato group coordinated with the trivalentnuclear t0 chromium atom contains less than 7 carbon atoms in analiphatic group and in which the aliphatic group also contains a highlyfunctional group 0.0l-0.5 parts water soluble hydrophilic colloid0.005-0.05 parts emulsion stabilizer.

10. A glass structure and a coating on the surfaces of the glass toprotect the surface and to render the surface more highly receptive toresinous materials combined therewith in the manufacture ofglass-resinous structures in which the coating comprises the combinationof the following materials in parts by weight:

0.25-5 .0 parts saturated polyester resin formed essentially of asaturated dibasic acid and a dihydric alcohol 0.01-20 parts cationicamine lubricant 0.l-2.0 parts Werner complex compound in which thecarboxylat-o group coordinated with the trivalent nuclear chromium atomcontains less than 7 carbon atoms in an aliphatic group and in which thealiphatic group also contains a highly functional group 0.01-0.5 partsof water soluble hydrophilic colloid 0.005-005 parts emulsion stabilizer0.0l-l.0 parts of an organo silane and hydrolysis product thereof inwhich the silane has an organic grou attached directly to the siliconatom having less than 7 carbon atoms and containing a highly functionalgroup.

11. Glass fibers and a coating on the glass fiber surfaces to protectthe glass fibers and to render the glass fibers more easily wet out withpolyester resins and to improve the bonding relation between thepolyester resins and the glass fiber surfaces in which the coatingconsists essentially of the combination of the following materials inparts by weight:

0.25-5.0 parts saturated polyester resin formed essentially of asaturated dibasic acid and a dihydric alcohol 0.01-2.0 partsmethacrylato chromic chloride 0.1-2.0 parts cationic amine lubricant0.0l-0.5 parts polyvinyl alcohol 0.01-1.0 parts of an organo silane andhydrolysis product thereof in which the silane has an organic groupattached directly to the silicon atom containing less than 7 carbonatoms and a highly functional group 0.005-0.05 parts of a co-genericmixture of conjugated polyoxyethylene-polyoxypropylene compounds on apolybasic carboxylic acid having a molecular weight less than 200 inwhich the polyoxy-ethylene groups are present in amounts ranging from20-90 percent by weight of the compound and in which the molecularWeight of the compound is at least 900.

12. In a product formed of glass fibers and a resinous material, theimprovement which consists of a coating directly on the glass fibersurfaces to protect the glass fibers and to enhance the bondingrelationship between the resinous material and the glass fiber surfacesin which the coating consists essentially of the following ingredientsset forth in the proportions by weight:

0.25-5.0 parts by weight saturated polyester resin in an uncured andsoluble state formed by the condensation reaction of a saturate-dpolyhydric alcohol and a saturated polybasic acid and in which thesaturated polyester resin is a partly reacted polyester resin whenformed by reaction of a saturated polyhydric alcohol other than adifunctional alcohol and a polybasic acid other than a dibasic acid0.1-2.0 parts by weight of a cationic amine lubricant 0.1- parts byweight of a Werner complex compound in which the carboxylato groupcoordinated with the trivalent nuclear chromium atom is formed with anorganic group containing less than 7 carbon atoms in aliphaticarrangement and a highly functional group 001- parts by weight of awater soluble hydrophilic col oid 0.005-005 parts by weight of anemulsion stabilizer.

13. In a product formed of glass fibers and a resinous material, theimprovement which consists of a coating directly on the glass fibersurfaces to protect the glass fibers and to enhance the bondingrelationship between the resinous material and the glass fiber surfacesin which the coating is formed of the following ingredients set forth inthe proportions by weight:

0.25-5.0 parts by weight saturated polyester resin formed essentially bythe condensation reaction of a saturated dibasic acid and a dihydricalcohol 0.1-2.0 parts by weight of an amine lubricant 0.l-l0.0 parts byweight of a Werner complex compound in which the carboxylato groupcoordinated with the trivalent nuclear chromium atom is formed with anorganic group containing less than 7 carbon atoms in aliphaticarrangement and in which the aliphatic group also contains a highlyfunctional group 0.0l-0.5 parts by weight polyvinyl alcohol 0.005-0.05parts by weight stabilizer in the form of a co-generic mixture ofconjugated polyoxyethylenepolyoxypropylene compounds on a polybasiccarboxylic acid having a molecular weight less than 200 in which thepolyoxyethylene groups are present in amounts ranging from 20-90 percentby weight of the compound and in which the molecular weight of thecompound is at least 900 99.535-82.45 parts by weight water.

14. In a product formed of glass fibers and a resinous material, theimprovement which consists of a coating directly on the glass fibersurfaces to protect the glass fibers and to enhance the bondingrelationship between the resinous material and the glass fiber surfacesin which the coating consists essentially of the following ingredientsset forth in the proportions by weight:

0.25-5.0 parts by weight saturated polyester resin formed essentially bythe condensation reaction of a saturated dibasic acid and a dihydricalcohol 0.1-2.0 parts by weight of an amine lubricant 0.1-10.0 parts byweight methacrylato chro-mic chloride 0.0l-0.5 parts by weight watersoluble hydrophilic colloid 0.005-0.05 parts by weight emulsionstabilizer 99.535-82.45 parts by weight water.

15. In a product formed of glass fibers and a resinous material, theimprovement which consists of a coating directly on the glass fibersurfaces to protect the glass fibers and to enhance the bondingrelationship between the resinous material and the glass fiber surfacesin which the coating consists essentially of the following ingredientsset forth in the proportions by weight:

0.255.0 parts by weight saturated polyester resin in an uncured andsoluble state formed by the condensation reaction of a saturatedpolyhydric alcohol and a saturated polybasic acid and in which thesaturated polyester resin is a partly reacted polyester resin whenformed by reaction of a saturated polyhydric alcohol other than adifunctional alcohol and a polybasic acid other than a dibasic acid 0.01-2.0 parts by weight of a cationic amine lubricant 0.1-2.0 parts byweight of a Werner complex compound in which the carboxylato groupcoordinated with the trivalent nuclear chromium atom contains less than7 carbon atoms in an aliphatic group and in which the aliphatic groupalso contains a highly functional group 0.01--0.5 parts by weight watersoluble hydrophilic colloid 0.005-0.05 parts by weight of an emulsionstabilizer 0.0l-l.0 parts by weight of an organo silane and hydrolysisproduct thereof in which the silane has an organic group attacheddirectly to the silicon atom having less than 7 carbon atoms andcontaining a highly functional group 99.6l-89.45 par-ts by weight water.

16. In a product formed of glass fibers and a resinous material, theimprovement which consists of a coating directly on the glass fibersurfaces to protect the glass fibers and to enhance the bondingrelationship between the resinous material and the glass fiber surfacesin which the coating consists essentially of the following ingredientsset forth in the proportions by weight:

0.25-5.0 parts by weight saturated polyester resin formed essentially bythe condensation reaction of a saturated dibasic acid and a dihydricalcohol 0.0 l-2.0 parts by weight of a cationic amine lubricant 0.1-2.0parts by weight of a Werner complex compound in which the carboxylatogroup coordinated with the trivalent nuclear chromium atom contains lessthan 7 carbon atoms in an aliphatic group and in which the aliphaticgroup also contains a highly functional group 0.010.5 parts by weightwater soluble hydrophilic colloid 0005-005 parts by weight of aco-generic mixture of conjugated polyoxyethylene-polyoxypropylenecompounds on a polybasic carboxylic acid having a molecular weight lessthan 200 in which the polyoxyethylene groups are present in amountsranging from 20-90 percent by weight of the compound and in which themolecular weight of the compound is at least 900 0.01l.0 parts by weightof an organo silane and hydrolysis product thereof in which the silanehas an organic group attached directly to the silicon atom having lessthan 7 carbon atoms and containing a highly functional group 99615-8945parts by weight water.

17. In a product formed of glass fibers and a resinous material, theimprovement which consists of a coating directly on the glass fibersurfaces to protect the glass fibers and to enhance the bondingrelationship between the resinous material and the glass fiber surfacesin which the coating consists essentially of the following ingredientsset forth in the proportions by weight:

025-5 .0 parts by weight saturated polyester resin in an uncured andsoluble state formed by the condensation reaction of a saturatedpolyhydric alcohol and a saturated polybasic acid and in which thesaturated polyester resin is a partly reacted polyester resin whenformed by reaction of a saturated polyhydric alcohol other than adifunctional alcohol and a polybasic acid other than a dibasic acid0.01-2.0 parts by weight of a cationic amine lubricant 0.1-2.0 parts byweight of a Werner complex compound in which the carboxylato groupcoordinated with the trivalent nuclear chromium atom contains less than7 carbon atoms in an aliphatic group and in which the aliphatic groupalso contains a highly functional group 0.01-0.5 parts by weightpolyvinyl alcohol 0.005-0.05 parts by weight of a co-generic mixture ofconjugated polyoxyethylene-polyoxypropylene compounds on a polybasiccarboxylic acid having a molecular weight less than 200 in which thepolyoxyethylene groups are present in amounts ranging from 20-90 percentby weight of the compound and in which the molecular weight of thecompound is at least 900 001-10 parts by weight of an organo silane andhydrolysis product thereof in which the silane has an organic groupattached directly to the silicon atom having less than 7 carbon atomsand containing a highly functional group 99.6l5-89.45 parts by weightwater.

18. In a product formed of glass fibers and a resinous material, theimprovement which consists of a coating directly on the glass fibersurfaces to protect the glass fibers and to enhance the bondingrelationship between the resinous material and the glass fiber surfacesin which the coating is formed of the following ingredients set forth inthe proportions by weight:

0.255.0 parts by weight saturated polyester resin formed essentially bythe condensation reaction of a saturated dibasic acid and a dihydricalcohol OBI-2.0 parts by weight methacrylato chromic chloride 0.1-2.0parts by weight of a cationic amine lubricant 0.011.0 parts by weight ofan organo silane and hydrolysis product thereof in which the silane hasan organic group attached directly to the silicon atom containing lessthan 7 carbon atoms and a highly functional group 0.0050.05 parts byweight of a co-generic mixture of conjugated.polyoxyethylene-polyoxypropylene compounds on a polybasic carboxylicacid having a molecular weight less than 200 in which thepolyoxyethylene groups are present in amounts ranging from 20-90 percentby weight of the compound and in which the molecular weight of thecompound is at least 900 99.61589.45 parts by weight water.

References Cited by the Examiner UNITED STATES PATENTS 2,392,805 1/1946Biefeld 1 17-126 2,674,619 4/ 1954 Lundsted 260-334 2,688,007 8/1954Steinman 117-126 2,801,189 7/1957 Collier 117-126 3,081,195 3/1963Biefeld et al 117126 OTHER REFERENCES Elvanol Polyvinyl Alcohols, issuedby E. I. du Pont de Nemours and Co. (Inc.), Wilmington, Del. (page 20).

RICHARD D. NEVIUS, Primary Examiner.

JOSEPH B. SPENCER, Examiner.

R. B. MURRAY, R. S. KENDALL, Assistant Examiners.

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